Textile assistant



United rates Patent 3,ti56,744 TEXTILE ASHSTANT .ioseph P. Copes and George M. Gantz, Easton, Pa, as-

signors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawin Filed Sept. 18, 1957, Ser. No. 684,660 '7 Claims. (Cl. 2528.8)

The present invention relates to textile assistants and particularly to thixotropically thickened and compounded mineral oils which may be emulsified in water.

It is well known that mineral oil when applied to textile fibres imparts desirable properties such as lubricity which add to the convenience of manufacture such as in carding, weaving, spinning, winding, transport, knitting, sorting, etc. whereby Wear on the machinery is reduced, the slippage of the fibres allows manufacturing with more efficiency, results in less loss of strength due to breakage of fibres, etc.

It is also well known that many additives for the mineral oil have been advocated which result in greater lubricity, more prevention of wear, less corrosion, greater ease of handling, less static electricity and many other benefits, and these additives include various compositions of matter such as organic acids and various salts and soaps thereof, of which might be mentioned various alkali and alkali earth metal salts of various longer chain fatty acids; various alcohols, amines, sulfonates, ethers, esters, various organic and inorganic chemical compounds containing phosphorus, arsenic, sulfur and others, various ethoxylated materials, many poly-functional type compounds and others too numerous to mention. It is thought that many of these materials, due to their polar nature and chemical reactivity are able to form films on the fibres and the metal parts and thus result in greater lubricity, resistance to abrasion, resistance to corrosion, resistance to soiling, and the deleterious effects of the various elements of the environment.

It is an object of the present invention to provide new and useful assistants for textile fibres.

Other objects and new and useful features will become more clearly apparent from the following description.

In order to study and investigate textile assistants, we have noted that among the more efiicacious materials employed, are the various esters of phosphoric acids. These compounds conform to the general formulae:

[It-(O ontonur-o r and wherein R represents an aliphatic or an aromatic radical, i.e. substituted or unsubstituted, containing from 8 to carbon atoms, 12 represents an integer of from 4 to and X represents either hydrogen, an alkali metal salt, ammonium group or an organic base, e.g. monoethanolamine, diethanolamine, triethanolamine, cyclo hexylamine, N-(1 amino-ethyl)morpholene, octylamine, oleylamine, stearylamine, etc.

The esters characterized by the foregoing general formulae are readily prepared by the reaction of polyphosphoric acid, phosphorus oxychloride, phosphoric acid or phospholen with any alcohol or phenol containing from 8 to 30 carbon atoms under conditions of mildly elevated temperatures and usually with the distillation of water formed in the reaction. If mixed esters are desired the reaction may be carried out stepwise.

The solubility will depend on the configuration of the molecule, the more highly ethoxylated materials being more water soluble, the lower members having greater oil solubility, and the formation of the metallic salt or amine salt usually results in a more water soluble product. Within these limits the molecule may be more tailored and fit individual requirements as will be discussed later.

The phosphate esters of polyoxyethylenated straight and branched chain aliphatic and aromatic alcohols, phenols, amines, etc. are readily prepared by the usual esterification procedure while employing polyphosphoric acid, P O .H O which is a partially dehydrated phosphoric acid at atmospheric pressure and at a temperature of about 115 C. for a period of four hours.

Various other means are also available. For example, phosphorus oxychloride (POCl may also be used, especially for monoand diesters. Phosphorus pentoxide is another reagent. Phosphorus trichloride results in phosphines. The degree of esterification depends largely on the mole ratio of the reactants although the nature of the reactants and the reaction conditions also influence the results. For monoesters, a 1:1 ratio of reactants is used. For diesters, a ratio of 2 moles of the hydroxy compound to 1 mole of the phosphorus compound is used. For triesters, a ratio of 3 moles of the hydroxy compound to 1 mole of the phosphorus compound is used.

The polyoxyethylenated straight and branched chain aliphatic and aromatic alcohols, phenols, amines, etc. which are to be converted to the phosphate esters as above described may readily be obtained by condensing the corresponding alcohol, phenol, amine, etc. which is desired to ethoxylate with from 1 to 40 moles of ethylene oxide. Processes for effecting such ethoxylation are well known in the art. In a preferred process, the base material which contains an active hydrogen atom, e.g. alcohol, phenol, amine, acid, etc. is made slightly basic by the addition of a suitable base such as KOH and is then treated while heating slightly with ethylene oxide under pressure until the desired amount of ethylene oxide has been condensed. This reaction proceeds readily and when the desired amount of ethylene oxide has been condensed with the base material the KOH or the like is neutralized and if desired any salt formed may be removed.

The thus obtained ethoxylated product may be esterified with polyphosphoric acid, phosphorus oxychloride, etc. as outlined above and as exemplified below, and the salt of the thus obtained phosphoric acid esters may be prepared by adding appropriate bases such as sodium hydroxide, calcium hydroxide, ethanolamine and the like.

The following examples illustrate the preparation of these phosphoric acid esters.

EXAMPLE A The condensation product of nonyl phenol with 4 molecular proportions of ethylene oxide were dissolved in ethylene dichloride as a solvent and stirred while a molar amount of POCl was added for a 39 minute period. This was then heated at reilux for a total of 12.2 hours and the reaction mixture was steam distilled. The desired phosphate ester was obtained in about 86.2% yield.

EXAMPLE B The condensation product of a mixture of C and C unsaturated aliphatic alcohols in which the C alcohols predominated, obtained under the trademark Ocenol, with 8 molar proportions of ethylene oxide was reacted with POCl 2 moles of the ethoxylated product and 1 mole of POCl being used, by mixing the two reactions together while heating at from 27 to C. for 23 hours 3 and then at 100 to 147 C. for an additional 5 hours. A very viscous liquid product was obtained in 98.3% yield.

EXAMPLE C The condensation product of straight chain fatty alcohols, predominately C alcohol, with 4 molar proportions of ethylene oxide was reacted in the ratio of 3 moles of the ethoxylated product with 2 mole of POCl by heating from 50 to 98 C. for 9 hours and then 110 to 148 C for 6.3 hours. Nitrogen gas was then bubbled through the reaction mixture to remove HCl. The phosphate ester was obtained in 99.1% yield.

The foregoing experiment was repeated using an equivalent amount of polyphosphon'c acid in place of the POC1 On completion of esterification the sodium salt was prepared which had a viscosity of 80.14 centipoises at 25 C.

EXAMPLE D The phosphate ester of oleyl alcohol was prepared by refluxing for 7 hours 2 molar proportions of oleyl alcohol and 1 molar proportion of P in benzene. The phosphate ester was obtained in a yield of 76.3%.

As examples of aliphatic and aromatic alcohols and phenols, whether substituted or unsubstituted, the following are illustrative: I-decanol, cetyl alcohol, octadecyl alcohol, ceryl alcohol, myricyl alcohol, d-citronellol (3,7- dimethyl-A6-octenol), 'r-rhodinol (3,7dimethyl-6-octene- I-ol), cis-3,S-dimethylcyclohexanol, 1,2,5-trimethylcyclopentanol, 2,3,4 trimethylcyclopentanol, 1,3,5 trimethylcyclohexanol, 2,4-xylenol, thymol, a-naphthol, fi-naphthol, glycol, trimethylene glycol, propylene glycol, glycerol, i-erythritol, xylitol, rhamnitol, dulcitol, d-manitol, d-soribitol.

While the phosphate esters prepared from polyoxyethylenated organic hydroxy compounds, e.g. alcohols and phenols, are preferred, it is to be understood that in place of the polyoxyethylenated alcohols and phenols mentioned above, polyoxyethylenated derivatives of other organic compounds containing an active hydrogen may be employed in the production of phosphoric acid esters. The number of such polyoxyethylenated derivatives are known in the art, being described for example in U.S. Patent 1,970,578 and include polyoxyethylenated derivatives of amines, amides, carboxylic acids and the like.

As specific illustrations of the phosphoric acid esters (other than polyphosphates whose exact structure is difiicult to portray) prepared from the foregoing alcohols and phenols, the following are representative:

O @ioomcmm ooHm .in OH ONa We have now discovered that such compounded mineral oils together with any one of the foregoing esters of phosphoric acid become thixotropically thickened by the addition of N-substituted 'y-hydroxy carboxylic acid amides characterized by the following general formula:

wherein R represents either hydrogen or a methyl group, and R represents an organic radical, devoid of water solubilizing groups such as sulfonic or carboxylic acids, containing from 10 to 30 carbon atoms, e.g. decyl, undecyl, undecylenyl, hendecyl, dodecyl, tridecyl, tetradecyl, cetyl, myristolenyl, pentadecyl, heptadecyl, hexadecyl, hexadecenyl, octadecyl, octadecenyl, octadecadienyl, abietinyl, dehydroalbietinyl, dihydroabietinyl, oleyl, elaidyl, erucyl, nonylbenzyl, octabenzyl, dimethylbenzyl, dioctabenzyl, etc. and mixtures of such radicals.

The compounds characterized by the foregoing general formula are obtained by the reaction of approximately 1 mole of an organic primary amine containing at least 10 carbon atoms or mixtures of such amines with 1 mole of either 'y-butyrolactone or y-valerolactone at a temperature of 80 to 95 C. as disclosed in application Serial No. 625,224, filed on November 30, 1956, now abandoned, by Fred B. Woodward et al. for N-Substituted Hydroxycarboxylic Acid Amides, the complete disclosure of which is incorporated herein by reference to the various compounds per se and to the methods of preparing the same.

As illustrative examples of the thixotropic thickening agents utilized in the preparation of the novel textile assistant in accordance with the present invention, the following may be mentioned:

OH OH3-H-OH2 CH2C ONHOHZ(CHZ)EOH1 The reaction product of N-decylamine and 'y-valerolactone.

(3 HO-CH CH CH CONHCH (CH CH The reaction product of N-dodecylamine and 'y-butyrolactone.

(4) HO-CH CH CH CONHCH (CH CH The reaction product of N-cetylamine and y butyrolactone.

(5) HO-CH CH CH CONHCH CH CH The reaction product of octadecylamine and 'y-butyrolactone.

octadecenylamine 35%, octadecadienylamine 45%.

(7) The reaction product of 1 mole (86.1 grams) of 'y-butyrolactone and 1 mole (365 grams) of a commercially available mixture of amines (derived from tall oil) and having the following composition: Octadecenylamine 15%, octadecadienylamine 15%, abietylamine 70%.

(8) The reaction product of 1 mole (86.1 grams) of 'y-butyrolactone and 1 mole (276 grams) of a commercially available mixture of amines having the following composition: hexadecylamine 6%, octadecylamine 93%, octadecenylamine 1%.

(9) The reaction product of 1 mole (86.1 grams) of 'y-butyrolactone and 1 mole (317 grams) of a commercially available primary amine made from a modified rosin (dehydroabietylamine) having the following formula:

on3 on CH CH3 (10) The reaction product of 1 mole (100.1 grams) of 'y-valerolactone and 1 mole (365 grams) of a commercially available mixture of amines having the following composition: octadecenylamine octadecadienylamine 15%, abietylamine 70%.

(11) The reaction product of 0.2 mole (7.2 grams) of 'y-butyrolactone with 0.2 mole (58.9 grams) of the monoamide prepared from coconut oil and ethylened-iamine in the usual manner.

(12) The reaction product of 1 mole (86.1 grams) of 'y-butyrolactone with 0.2 mole (65.3 grams) of stearamidoethyl amine.

(13) The reaction product of 0.5 mole (43 grams) of -butyrolactone with 0.48 mole (320 grams) of polymerized fatty acid octaethylene amine. The latter is derived from an acid available on the market under the brand name of Empol 1022 and is derived from essentially a C dibasic acid resulting from the polymerize; tion of naturally occurring unsaturated C fatty acids. The general properties are as follows:

Molecular weight approx 600 Acid value, mg. KOI-I/g min 180 Saponification value, mg. KOH/ g min 185 Neutralization equivalent 289-304 Dimer content percent 75 Trimer content do 22 Monomer content do.. 3 Sp. gr. 15.5 C 0.95 Viscosity at 25 C centistokes 10,000

14) The reaction product of 1 mole of v-butyrolactone tone with 1 mole of a commercially available mixture of amines having the following composition: octylamine 8%, decylamine 9%, dodecylamine 47%, tetradecylamine 18, hexadecylamine 8%, octadecyl 5% and octadecenyl 5%.

(15) The reaction product of 1 mole of 'y-butyrolactone with 1 mole of a commercially available mixture of amines having the following composition: dodecylamine 90%, tetradecylamine 9% and octadecenylamine 1%.

(16) The reaction product of 1 mole of 'y-butyrolactone with 1 mole of a commercially available mixture of amines having the following compositions; dodecylamine 4%, tetradecylamine 90, hexadecylarnine 4% and octadecenylamine 2%.

The compounds illustrated by Examples I to XII of the aforementioned patent application as well as all the compounds disclosed in application Ser. No. 625,234, filed November 30, 1956, by R. L. Mayhew and J. P. Copes for Lubricating Grease Compositions may also be used for the purpose of the present invention. The disclosure and teachings of the latter applications are also incorporated herein by reference thereto.

The thickening agents may be employed in any type of mineral oil currently used in the finishing of textile fibres in an amount ranging from 0.1% to about 50% by weight of the mineral oil. In the actual preparation of the textile assistant, the mineral oil is first compounded with any one of the foregoing esters of phosphoric acid and then the thickening agent added and the mixture heated to about 70-100 C. followed by cooling. The compounded mineral oil is then ready for application to textile fibres by doctoring, padding, spraying, brushing or other conventional means. The unusual feature of the compounded mineral oil thus prepared is that it may be advantageously emulsified in water with or without the addition of a minor amount of an emulsifying agent depending upon the nature or character of the phosphate ester added. This unusual feature renders the use of the additives to the mineral oil much more practical and controllable in that the amount of the additive may be reduced to a quantity which is actually necessary for the function expected; the amount applied becomes much more certain and the uniform distribution of the material throughout the textile interstices is assured.

Among the emulsifiers found of practical use in this connection may be mentioned nonionic surfactants. Paradoxically, while one would expect a rather low mole ratio ethoxylated nonionic material to be effective here, and while such materials may be used, it has been found that the normally more water types of nonionics are especially effective and these, in the presence of the thickening agents above described, are able to exist homogeneously dispersed or dissolved in the organic phase. This peculiarity is of great value in the present invention because the entire system including the hydrocarbon, the additive, the thickening agent and the emulsifier may be compounded completely and accurately beforehand, and may be emulsified with water at will in any amount without cumbersome calculations by the textile mill operator, and having been applied to the textile, will evaporate the volatile component (water) and in this process, will result in no untoward phase separations or heterogeneous masses. A secondary advantage is that certain additives which are desirable but which may not be compatible with mineral oil alone may become compatible when the thickening agent is present. A tertiary benefit may be that, in certain cases, the additive may be also the emulsifier.

The amounts of each constituent will vary considerably depending on the application. For purposes of economy it is desirable that the organic formulation be largely mineral oil and successful compositions have been prepared where the mineral oil has ranged up to about 96%, a useful, practical range being say from 50% to about 98%, a preferred range being between and 98%. The mineral oils preferred in formulating the products of this invention preferably have a viscosity in the range of 50 to 355 at 100 F. (378 C.), and more preferably 50 to 200 at 100 F.

The amount of phosphate ester may range from 1 to 10% based on the Weight of the organic material to be treated, the preferred range however being from 1 to 5 The phosphoric acid ester may range from 1 to 10% with a preferred range of 1 to 5%. The emulsifying agent may range from 0 to 5% usually in the preferred range of 1 to 2%.

The application to the textile will range between 0.1% to 2 or 3% depending on the eifects desired. To apply the composition through water emulsion, an amount ranging from 1 to 10 or 20% will be added, the balance being water. This will be applied to the textile and allowed to dry.

The textile may be natural materials such as cotton, wool, silk, hemp, jute, flax, hair, leather, milkweed down,

and others, and synthetic materials such as rayon, cellulose, polymeric materials such as nylon and others.

In order to disclose the invention in greater detail, the following examples are furnished. It is to be clearly understood however, that these examples are merely illustrative and are not intended to limit the scope of the invention as claimed.

Rather than to attempt to offer textile mill production reports which are extremely difficult to evaluate inasmuch as in many cases these are highly subjective and possibly limited to the foremans opinion that this is better, or to attempt to gauge production figures which are complicated by variable circumstances often relatively beyond reasonable control and which have little direct relationwould correspond to glass and ceramic guides for the yarn; a steel cylinder which would represent the metallic processing equipment including steel guides, needles, carding equipment and others; and a yarn wound cylinder which yielded values related to the internal friction of yarns and materials and was indicative of performance in the operations of winding, carding, spinning, knitting, weaving, sewing, wearing, etc.

Thus the following exemplary information was obtained, the indicated amounts of additive was added to yarn, the percentage being of the weight of the yarn, the yarn being acetate rayon, the cylinder being glass, temperature being about 75 F. and the relative humidity being about 50%.

Grams of force, yarn to glass Application, Formula Percent ft./m. 200 800 1,100 1,300

it./min. ft./min. ftJmin. ft./min.

0 Plain yarn blank 15.0 26. 0 28.0 26.0 26.0 4 Mineral oil alone (Bayol 50) 15.0 26. 30. 0 29. 0 1 28.0 Mineral oil alone (Bayol 50) 15.0 25.0 43. 0 44. 0 1 44. 0

1 Sodium salt of phosphoric acid diesterified with 1 mole of oleyl alcohol and 8 moles of ethylene oxide 3 16.0 26.0 27. 5 32.0 2 9.0 1 Sodium salt of phosphoric diester of 1 mole of a 12 carbon atom alcohol reacted with 4 moles of ethylene oxide 16.0 29.0 34. 0 5 36.0 1 Nonionie surfactant prepared by reacting 1 mole of nonyl phenol with 10 moles of ehtylene oxide 16.0 26. O 27.0 30.0 4 85% Mineral oil phosphoric acid triester of: a C12 (average) alcohol reacted with ethylene oxide in the ratio of 1 mole of alcohol to 4 moles of ethylene oxide 16. 0 16.0 20.0 18.0 3 19. 0

Grams of force, orlon, yarn to yarn 5 97% of Mineral oil 1%(% of nonionic surfactant obtained by condensing 1 mole of nonyl phenol with 10 moles of ethylene oxide (1.5% of the thickener of illustration 14) 13 13 13 13 13 1 Data indicate mineral oil results in more friction, and the more mineral oil, the more friction. 2 These data indicate that the additives alone are inferior as lubricants because the friction is greater. 3 It is readily apparent that the lubricity additive and the mineral oil together result in much less friction.

ship to the textile auxiliary under scrutiny such as weather, power, heat, light, morale, etc., it was deemed best to exemplify the present invention by objective scientific data.

Accordingly frictional forces were measured by attaching a yarn to a strain gauge, passing the yarn about a rotatable cylinder, applying tension to the yarn to cause the yarn to apply pressure to the cylinder, rotating the cylinder and noting the friction by reading the force operating upon the strain gauge. It was possible to use various yarns in this way, the yarns might be or might not be impregnated with lubricant, the cylinder might be of glass, ceramic, steel, brass or other material, and the cylinder might be wound with yarn so that a yarn to yarn frictional force could be determined. In this way the various lubricants could be evaluated and the differences among them could be noted. These differences correlated very Well with long term experience in the plant under actual in- Example I The following mixture was prepared by the addition in the order given:

Percent Light mineral oil having a viscosity of 7 cps. at 25 C 57 Nonionic surfactant obtained by condensing 1 mole or dustrial manufacturing conditions. 60 nonyl phenol with 10 moles of ethylene oxide 1 In the test data which follow in the illustrative working Phosphoric i di t f dinonyl phenol with 4 moles examples, a rate is given for the rotation of the cylinderof ethylene oxide 38 This rate is expressed in linear surface feet per minut Thickener of illustration 3 4 and when the figure 0 is used it means that the cylinder was rotated extremely slowly and a reading of strain was made as a maximum value before motion started, the interval being explained by the lightening and stretching of the yarn before motion (slippage) started, and the Feet per minute: Grams of force figure represents an expression of static friction. The 0 15 friction is expressed as grams of force and is O tained by 200 18 winding the yarn one quarter turn the cylind r (c ging 800 20 the direction 90) and loading the yarn with 5 grams of 1100 20 mass. The figures expressed may be converted to dynes 1300 20 by use of the factor g (approx. 98).

Values were obtained using a glass cylinder which 9 that the presence of the thickening agent tremendously contributes to the low friction of the Dacron fibre.

10 Example V The following mixture was prepared by the addition in the order given:

Exam le II Percent Th f H t p d b th dd 5 Liglgt rineral oil having a viscosity of 1D cps. at 70 e 0 owing mix ure Was prepare y e a mom in the order given: Nonionic surfactant obtained by condensing 1 mole Percent of dinonyl phenol with moles of ethylene Light mineral oil having a viscosity of 7 cps. at C- Oxide 1 Ph h i acid diester f 1 mole f dinonyl phenol 10 Phosphoric acid drester of oleyl alcohol with 8 moles With 4 moles of ethylene oxide 37 f elhylene oxlde 38 Thickener of illustration 4 3 Thlckenel' 0f lllustratloll The foregoing mixture was heated to 59 C. and According to the above method acetate yarn with the u cooled at room temperature. After cooling, the material foregoing composition gave the following values of force xists as a firm gel and is slightly opaque. It may be at various speeds: applied directly to textile fibres or can be stably emulsified by the addition of Water and then applied to the tex- Feet per minute: Grams of force tile fibre.

0 16 The material is sufiiciently gelled so that it does not 200 16 20 flow under the force of gravity, as when the container 20 is inverted. Upon agitation much of the gelled nature 1100 18 is lost and the material will flow. Upon further stand- 00 19 ing, the material reverts gradually to the more gelled cOnsistency. When applied to fibres such as filaments, yarns, H Example 1H tows, hairs, bristles, etc. the material causes, cohesion among the individual fibres and strands. Vthen such Example Il was repeated with the exception that the fibres or strands are sub ected to motion, l quefaction of thickener of illustration 4 was replaced by the thickener the gelled material ensues followed by lubr cation. of illustration 5. The results obtained are as follows: W acetate Y the fol'egolng comPosltlon gal/E the following values of force at the various speeds: Feet gar minute: Grams of tori; Feet minute; Grams of force o 14 388 16 /2 200 15.5 1100 20 35 800 16 18 1100 16 1300 19 1300 165 Example VI Example 1V 4 The following 16 compositions were prepared by como 0 bining all three ingredients, warming and cooling. Most fi gfifgz Z; i figz i g?z iig ig ggg i ffi? i g gf of the systems were clear solutions at 60 C. Exceptions en 11 t 8 Th u b f n c are: No. 2, dissolved at 25 C.; No. 6, dissolved at are 1 us fa Ion eresu s o tamed ale as 0 C.; No. 7, dissolved at C.; and No. 10, dissolved at C. Upon cooling, each became a thixotropic gel. Feet g mmute' Grams of 45 All of these compositions could be emulsified in water 2 15 5 with agitation. The more thixotropic emulsified more 00 readily. All, however, emulsified well when introduced to 800 the water in the melted state. Cold water was found 1100 16/2 satisfactory for this purpose. All emulsions were quite 1300 16 /2 50 stab1e Comp Thickening agent Amount Phosphate ester Amount Diluent No. percent percent 1 Thickener of illustration l 21 G O 2 "lhickener oi'il1ustrat10n2-. 4 (O1za1cohol-i-4EtO)zP\ 4 C ONa Thickener oiillustration 3..." 4 (C1ialcoho1+4EtO)aP-=O 4 O Thickener of illustration 4..-" 4 (C12 a1cohol+4EtO)3P:O 10 O gg ckener of llustrat on 5 4 (C12 a1cohol+4EtO aP=O 20 O ickener of illustration 6. 25 (Cm alcoho1+4EtO) P=O 25 C 7 Thickener of illustration 7....-. 4 (Nonyl phenol+4EtO)zP 0 8 Thickener of illustration 8 4 (Dinonylphenol+4EtO)zP 4 O 9 Thickeuer of illustration 9 4 (Dinonylphenoi+7EtO)P-OH 4.5 O

See footnotes at end of table.

Comp. Thickening agent Amount Phosphate ester Amount Diluent No. percent percent Thickener of ilustration 10 4 (Dinonylphenol-I-35Et0)P-OH 4 O 11 Thickener of illustration 11.-.- 4 (C11 alcohol+4EtO)aP=O 4 P 12 Thickener of illustration 12 4 (C12 alcohol+4EtO)aP=O 4 G 13 Thiekener of illustration 13.... 4 (C12 alcohol+4EtO)aP=0 4 0 l4 Thickener of illustration 14".. 4 (C11 alcohol+4Et0)aP=O 4 P 15 Thickener of illustration 15.-.. 4 (G12 alcohol+4EtO)aP=O 4 O 16 Thickener of illustration 16 .1 4 (C12 alc0hol+4EtO aP=O 4 0 NOTE .0 is carnation light mineral oil (Sonneborne) O is crankcase type lubricating mineral oil. P is light hydrocarbon fraction (B.P.=90100 0.).

We claim: 5. A thixotropically thickened textile assistant compo- A thlxotropically thickened textile asslstant composition according to claim 1 wherein the gelling agent com- 'Q comprising 50 i0 93% y Of a hYdI'OCHFbOII prises the reaction product of 1 mole of 'y-butyrolactone numeral 011 havlllg a saylqolt Viscoslty of to 355 f and 1 mole of a mixture of amines having the following 100 F., 1 to 10% by weight of an organic phosphoric 20 composition; acid ester of the class consisting of those of the following formulae: Percent 0 Octylamine 8 [R(O 01120112 n-o Decylamm? 9 .1 Dodecylamine 47 Tetradecylamine 18 and Hexadecylamme 8 Octadecylarnine 5 J3 Octadecenylamine 5 wherein R represents a member selected from the class consisting of alkyl and aryl groups of from 8 to 30 carbon atoms, n represents an integer of from 4 to and X represents a member selected from the class consisting of hydrogen, alkali metal, ammonium group; mono-, diand trialkanolamine, N-(l-aminoethyl) morpholene, octylamine, oleylamine and stearylamine, and from 0.1 to 50% by Weight of the said mineral oil of at least one gelling agent having the following general formula:

Ra-( JH-CHzOHzCONHR4 wherein R represents a member selected from the class consisting of hydrogen and methyl group, and R represents a member selected from the class consisting of aliphatic hydrocarbon radicals containing from 10 to 30 carbon atoms and an aralkyl hydrocarbon radical containing from 8 to 23 carbon atoms.

2. A thixotropically thickened textile assistant composition according to claim 1 wherein the gelling agent comprises the reaction product of 1 mole of 'y-butyrolactone and 1 mole of N-cetylamine.

3. A thixotropicaliy thickened textile assistant composition according to claim 1 wherein the gelling agent comprises the reaction product of 1 mole of 'y-butyrolactone and 1 mole of octadecylamine.

4. A thixotropically thickened textile assistant composition according to claim 1 wherein the gelling agent comprises the reaction product of 1 mole of 'y-butyrolactone and 1 mole of a mixture of amines having the following composition:

Percent Hexadecylamine 6 Octadecylamine 93 Octadecenylarnine 1 6. A thixotropically thickened textile assistant compo sition according to claim 1 wherein the gelling agent comprises the reaction product of 1 mole of 'y-butyrolactone and 1 mole of a mixture of amines having the following composition:

Percent Dodecylamine Tetradecylamine 9 Octadecenylamine 1 7. A thixotropically thickened textile assistant composition according to claim 1 wherein the gelling agent comprises the reaction product of 1 mole of 'y-butyrolactone and 1 mole of a mixture of amines having the following composition: 

1. A THIXOTROPICALLY THICKENED TEXTILE ASSISTANT COMPOSITION COMPRISING 50 TO 98% BY WEIGHT OF A HYDROCARBON MINERAL OIL HAVING A SAYBOLT VISCOSITY OF 50 TO 355 AT 100*F., 1 TO 10% BY WEIGHT OF AN ORGANIC PHOSPHORIC ACID ESTER OF THE CLASS CONSISTING OF THOSE OF THE FOLLOWING FORMULAE: 